Liquid recording material

ABSTRACT

A liquid recording material containing at least a carrier liquid, a resin, a coloring agent, and a reactive silicone material, an image transfer sheet for use with the liquid recording material, and a method of fixing images, using the liquid recording material, are disclosed.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a liquid recording materialwhich may be used as a liquid developer such as an electrophotographicdeveloper, for use in wet-type recording apparatus such as anelectrophotographic apparatus, a printer, or for use in ink-jetrecording apparatus, and which liquid recording material may also beused as a printing ink.

[0003] 2. Discussion of Background

[0004] It is conventionally known that silicone resin is used as acomponent for an electrophotographic developer. For example, in JapaneseLaid-Open Patent Application 53-57039, there is disclosed a developmentmethod conducted by coating a development roller with a liquid developerwith a viscosity of 3 to 1,000 cp, a solid component content of 0.5 to50 wt. %, and a particle size of 0.5 to 5 μm (silicone toner with highviscosity and high solid component content, containing silicone oil withhigh viscosity).

[0005] Japanese Laid-Open Patent Application 3-171149 discloses asilicone toner prepared by using a vinyl polymer which contains across-linking agent in an amount of 0.005 wt. % or more.

[0006] Japanese Laid-Open Patent Application 3-171150 discloses asilicone toner which contains a rosin-based polymer with a molecularweight of 2000 to 40000 and a softening point of 50 to 190° C.

[0007] Japanese Laid-Open Patent Application 3-171151 discloses asilicone toner prepared by using a polymer which is prepared bycross-linking a carboxyl-group-containing vinyl polymer with amine.

[0008] Furthermore, Japanese Laid-Open Patent Application 3-200263discloses a silicone toner which contains erucamide.

[0009] Japanese Laid-Open Patent Application 3-200264 discloses asilicone toner containing a vinyl polymer with a weight-averagemolecular weight/number-average molecular weight ratio of 4 or more.

[0010] Japanese Laid-Open Patent Application 3-200265 discloses asilicone toner comprising a self-crosslinking polymer and a crosslinkedpolymer.

[0011] Japanese Laid-Open Patent Application 3-225356 discloses asilicone toner comprising a crosslinked polyester.

[0012] Japanese Laid-Open Patent Application 3-225357 discloses asilicone toner prepared by using a polymer with part of a main chain ora side chain thereof being connected by an acid-base mutual action.

[0013] Japanese Laid-Open Patent Application 3-225358 discloses asilicone toner prepared by using a methylol-group-containing resin and aresin which is reactive with the methylol-group-containing resin.

[0014] Japanese Laid-Open Patent Application 3-225361 discloses asilicone toner comprising a polyolefin with a melt index of 25 to 700.

[0015] Japanese Laid-Open Patent Application 3-225364 discloses asilicone toner comprising a polyolefin with an AV of 0.5 or more, and amelt viscosity of 50 to 15,000 cp at 200° C.

[0016] Japanese Laid-Open Patent Application 4-88357 discloses asilicone toner with a viscosity of 1 to 50 cp at 100° C. and a criticalsurface tension of 18 to 36 dynes/cm when the solid component thereof is10 wt. %.

[0017] Japanese Laid-Open Patent Application 3-199204 discloses a tonerprepared by using a silicone oil as a polymerization catalyst.

[0018] Japanese Laid-Open Patent Application 3-223302 discloses a methodof producing a toner by polymerizing a toner preparation material whichis prepared by dissolving or dispersing a vinyl monomer in a siliconeoil with a viscosity of 10000 CS or less.

[0019] Japanese Laid-Open Patent Application 3-292352 discloses the useas a toner of a non-aqueous dispersion liquid which contains a polymerwhich is prepared from at least (a) one resin which is insoluble insilicone oil and (b) a monomer which dissolves the resin.

[0020] Japanese Laid-Open Patent Application 3-171152 discloses a tonercomposed of a fluorine-based solvent, an aliphatic hydrocarbon and asilicone solvent.

[0021] Japanese Laid-Open Patent Application 4-199064 discloses the useof a concentrate toner by diluting the concentrate toner with a dilutionliquid comprising as the main component a silicone oil.

[0022] Japanese Laid-Open Patent Application 53-57039 discloses asilicone toner with a viscosity of 3 to 1000 CS, a solid componentcontent of 0.5 to 50 wt. %, and a particle size of 0.3 to 5 μm.

[0023] Japanese Laid-Open Patent Application 3-199204 and JapaneseLaid-Open Patent Application 3-223302 disclose a method of producing atoner by polymerizing a vinyl monomer in silicone oil.

[0024] Furthermore, there is known an electrophotographic liquiddeveloper which is prepared by dispersing a toner which comprises as themain components a thermoplastic resin such as styrene resin or acrylicresin, and a coloring agent comprising a pigment such as carbon black ora dye, in a carrier liquid such as silicone oil, vegetable oil, or analiphatic hydrocarbon solvent as disclosed, for instance, in JapaneseLaid-Open Patent Application 55-35321.

[0025] As a recording method, using the above-mentioned liquiddeveloper, there is known an intermediate-image-transfer recordingmethod comprising the steps of forming a latent electrostatic image onthe surface of a photoconductor, developing the latent electrostaticimage to a visible toner image with the liquid developer, transferringthe toner image to an intermediate image transfer belt, and transferringthe toner image to a recording sheet, as disclosed, for instance, inU.S. Pat. No. 4,708,460.

[0026] A method of directly transferring the toner image to therecording sheet, without using the intermediate image transfer belt, isalso known. In ink-jet inks and printing inks, water, various solvents,coloring agents, resins and dispersing agents are used.

[0027] The above-mentioned conventional recording methods using theliquid developers have the problems that when the boiling point of thecarrier liquid for use in the developers is high, for instance, when analiphatic hydrocarbon solvent such as silicone oil or a vegetable oil isused as the carrier liquid, the carrier liquid is held on the imagetransfer sheet and is difficult to evaporate, and the odor of thecarrier liquid stays particularly when the boiling point of the carrierliquid is high, and that image fixing cannot be performed properly.

[0028] The above-mentioned intermediate-image-transfer recording methodhas the shortcomings that image transfer efficiency is low, images withsufficiently high density cannot be obtained on a recording paper, andimages with clear contours cannot be obtained.

[0029] In the above-mentioned intermediate-image-transfer recordingmethod, the image transfer from the intermediate image transfer belt tothe recording sheet is carried out with the application of pressure toboth the recording sheet and the intermediate image transfer belt. Inorder to produce sufficient adhesion between the toner image and therecording sheet for use in practice, it is required to increase theabove-mentioned pressure. However, in apparatus used in practice, thereis a limit to the pressure that can be applied so that sufficientadhesion for use in practice cannot always be obtained and therefore theimage transfer efficiency is low.

[0030] In conventional copying machines and printers, a heat roller or aheat plate is used as a heat source for fixing toner images, so thatsuch conventional copying machines and printers have the shortcomingthat power consumption is large.

[0031] Furthermore, developers in which silicone oil is used as thecarrier liquid therefor have the shortcoming that they lack preservationstability because silicone oil is non-polar and therefore thedispersibility thereof is poor.

[0032] Furthermore, the use of silicone oil as a component forelectrophotographic developers and recording materials has beenconventionally proposed, for example, as disclosed in Japanese Laid-OpenPatent Applications 3-171149, 3-171151 and 3-171152, in which the use ofdimethyl silicone oil is specifically proposed.

[0033] However, cyclic polysiloxanes, for example, commerciallyavailable polysiloxanes (Trademark “KF994”, “KF995”, made by Shin-EtsuChemical Co., Ltd.), have a low molecular weight and a low viscosity, sothat the evaporation thereof is rapid, but have the problem of causingimproper electric contact.

[0034] On the other hand, silicone oils having high molecular weight,such as KF96-10CS, 50CS, 100CS, 300CS, 1000CS, 5000CS, and 50000CS, aredifficult to evaporate and therefore have no problem with respect toelectric contact, but remain in copying paper, and cause image fixingperformance to deteriorate, and ooze out of the copy paper, smearing thecopy paper. When toner images are formed on an OHP (overhead projector)film, using the above silicone oils, the toner images are difficult tofix and become sticky.

SUMMARY OF THE INVENTION

[0035] It is therefore a first object of the present invention toprovide a liquid recording material which is capable of solving theabove-mentioned conventional problems when the carrier liquid with highboiling point is used, and has no environmental pollution problems, withthe safety to health taken into consideration.

[0036] A second object of the present invention is to provide arecording material which has the features of the above-mentioned liquidrecording material and is capable of forming toner images with asufficiently high density for use in practice and with clear contours ona recording sheet, with the application of small pressure thereto in arecording apparatus using the above-mentioned intermediate imagetransfer method.

[0037] A third object of the present invention is to provide a recordingmaterial with the features of the above-mentioned recording materials,and also with the features that the above-mentioned improper electriccontact is not caused, and the silicone oil is prevented from oozingfrom the copying paper after coping or printing, and images with highimage quality can be obtained with high dot reproduction.

[0038] A fourth object of the present invention is to provide an imagetransfer material for use with the above recording material.

[0039] A fifth object of the present invention is to provide a method ofpromoting the fixing of images developed by the above liquid recordingmaterial of the present invention.

[0040] The first to third objects of the present invention can beachieved by a liquid recording material comprising a carrier liquid, aresin, a coloring agent, and a reactive silicone material.

[0041] In particular, in the present invention, by use of the reactivesilicone material in the carrier liquid, the silicone oil is preventedfrom oozing from the copying paper after coping or printing, and theabove-mentioned improper electric contact can be prevented fromoccurring by the chemical reaction or physical adsorption of thereactive silicone material.

[0042] Further, by use of the reactive silicone material in the resinand/or the coloring agent, images with high image quality and high dotreproduction can also be obtained by the chemical reaction or physicaladsorption of the reactive silicone material.

[0043] In the above-mentioned liquid recording material of the presentinvention, it is preferable that the reactive silicone material comprisesuch a reactive silicone compound that contains in the molecule thereofat least one group selected from the group consisting of vinyl group,amino group, hydroxyl group, epoxy group, isocyanate group, and anactive hydrogen.

[0044] In the liquid recording material of the present invention, thereactive silicone material may be contained in at least one of thecarrier liquid, the resin, or the coloring agent.

[0045] The reactive silicone material for use in the carrier liquid, theresin and the coloring agent may comprise a silicone RTV rubber.

[0046] The carrier liquid may comprise the reactive silicone materialand a polymerizable vinyl monomer, with the weight ratio of the reactivesilicone material: the polymerizable vinyl monomer being in a range of(0.01 to 9): 1.

[0047] The carrier liquid may also comprise the reactive siliconematerial and at least one component selected from the group consistingof an aliphatic hydrocarbon, a vegetable oil, a synthetic oil, and asilicone oil.

[0048] The carrier liquid may further comprise a polymerizationinitiator.

[0049] The carrier liquid may further comprise at least one componentselected from the group consisting of a gelling agent and across-linking agent.

[0050] As the coloring agent for use in the present invention, forinstance, a yellow coloring agent, a magenta coloring agent, a cyancoloring agent, and a black coloring agent can be employed. The yellowcoloring agent may comprise a disazo pigment, the magenta coloring agentmay comprise a quinacridone pigment or a carmine pigment, the cyancoloring agent may comprise copper phthalocyanine, and the blackcoloring agent may comprise carbon black.

[0051] The liquid recording material of the present invention mayfurther comprise at least one component selected from the groupconsisting of an oxidizing agent, a reducing agent, an esterificationagent, a coupling agent, a gelling agent, and a polymerizationinitiator.

[0052] The fourth object of the present invention can be achieved by animage transfer material comprising at least on the surface thereof atleast one component selected from the group consisting of an oxidizingagent, a reducing agent, an esterification agent, a coupling agent, agelling agent, and a polymerization initiator.

[0053] The fifth object of the present invention can be achieved by amethod of fixing an image developed by using the above-mentioned liquidrecording material of the present invention which comprises the carrierliquid, the resin, the coloring agent, and the reactive siliconematerial, on the above-mentioned image transfer material of the presentinvention which comprises at least on the surface thereof at least onecomponent selected from the group consisting of an oxidizing agent, areducing agent, an esterification agent, a coupling agent, a gellingagent, and a polymerization initiator, with the application of coronacharge thereto as an external stimulus.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] As mentioned above, the liquid recording material of the presentinvention comprises the carrier liquid, the resin, the coloring agent,and the reactive silicone material.

[0055] The carrier liquid may comprise the reactive silicone materialand an aliphatic hydrocarbon.

[0056] Representative examples of the aliphatic hydrocarbon for use inthe carrier liquid are isododecane, isononane, and commerciallyavailable aliphatic hydrocarbon carrier liquid such as “Isopar G”,“Isopar H”, “Isopar L”, “Isopar M” and “Isopar V” (Trademarks), made byExxon Chemical Japan Ltd., which may be used in the form of a mixture.

[0057] The carrier liquid may also comprise the reactive siliconematerial and a vegetable oil.

[0058] Representative examples of the vegetable oil are soybean oil,cottonseed oil, safflower oil, sunflower oil, camellia oil, colza oil,Kanora oil, castor oil, linseed oil and olive oil.

[0059] When such vegetable oils are subjected to alkali purification,modification, or heat treatment, the pigment dispersibility thereof isso improved that image density, image resolution and image fixingperformance can be improved. It is preferable that such a dispersingmedium for the carrier liquid be a non-polar, highly insulating andodorless liquid.

[0060] The carrier liquid may also comprise the reactive siliconematerial and a synthetic oil.

[0061] Representative examples of the synthetic oil are fatty estersobtained by the reaction between higher fatty acid and alcohol, andester compounds obtained by the reaction between higher fatty acid andethylene glycol or glycerin.

[0062] The carrier liquid may also comprise the reactive siliconematerial and a silicone oil such as dimethyl silicone oil.

[0063] By use of the mixture of the reactive silicone material and thesilicone oil such as dimethyl silicone oil in the carrier liquid, thecost of the liquid recording material can be reduced, and the waterresistance and the solvent resistance of the liquid recording materialof the present invention can be improved.

[0064] The carrier liquid may also comprise the reactive siliconematerial and a polymerization initiator.

[0065] In this case, a small amount of an initiator, such as AIBN, BPO,ammonium persulfate or hydrogen peroxide, is added to the reactivesilicone material, and the reactive silicone material is polymerizedafter copies are made so that the image fixing performance can beimproved.

[0066] The carrier liquid may also further comprise at least onecomponent selected from the group consisting of a gelling agent and across-linking agent in addition to the reactive silicone material.

[0067] Representative examples of the gelling agent are12-hydroxystearic acid and calcium oleate, which may be added in anamount of about 0.1 to 20 parts by weight to 100 parts by weight of thecarrier liquid, whereby the dispersibility and the image fixingperformance of the recording material can be improved. The same effectas mentioned above can be obtained by using a cross-linking agentinstead of the gelling-agent.

[0068] The liquid recording material of the present invention mayfurther comprise at least one component selected from the groupconsisting of an oxidizing agent, a reducing agent, an esterificationagent, a coupling agent, a gelling agent, and a polymerizationinitiator.

[0069] As the oxidizing agent, for example, metal salts of naphthenicacid can be employed. As the reducing agent, for example, various kindsof metal powders, such as zinc powder, can be employed. As theesterification agent, for example, an acid or basic organic material canbe employed. As the coupling agent, a silane coupling agent and a metaltitanate coupling agent can be employed. As the polymerizationinitiator, for example, AIBN, BPO, PERBUTYL-O, and KAYAESTER-O can beemployed. By containing any of the above components in the liquidrecording material, the component reacts with the reactive siliconematerial in the recording material, so that the image fixing performanceand the dispersibility of the liquid recording material are improved.When a silicone oil is used in the recording material, theabove-mentioned components can prevent the silicone oil from staying inthe recording sheet.

[0070] Furthermore, the image transfer material of the present inventioncomprise at least on the surface thereof at least one component selectedfrom the group consisting of an oxidizing agent, a reducing agent, anesterification agent, a coupling agent, a gelling agent, and apolymerization initiator.

[0071] These components are capable of reacting with the liquidrecording material of the present invention, so that significantlyhighly improved image fixing performance can be attained when the imagetransfer material of the present invention and the liquid recordingmaterial of the present invention are used in combination.

[0072] The image developed by using the above-mentioned liquid recordingmaterial of the present invention can be fixed on the above-mentionedimage transfer material of the present invention with the application ofcorona charge thereto as an external stimulus. As the external stimulus,not only the corona charge, but also light such as UV and flash light,and heat from a heat roller or hot air can be employed. In this imagefixing method, oxidation polymerization is promoted, so that the imagefixing performance can be improved.

[0073] As mentioned above, the reactive silicone material for use in thepresent invention may comprise such a compound that contains in themolecule thereof at least one group selected from the group consistingof isocyanate group, Si—H group, vinyl group, amino group, hydroxylgroup, epoxy group, and methacryloxy group. Such reactive siliconematerials and reactive silicone compounds are commercially available.TABLE 1 shows representative examples of such reactive siliconematerials and compounds. TABLE 1 (1)

[FM1111, 1121 and 1125 (Trademarks), made by Chisso Corporation] (2)

[FM2231, 2241 and 2242 (Trademarks), made by Chisso Corporation] (3)

[FP2231, 2241 and 2242 (Trademarks), made by Chisso Corporation] (4)

[FM3311, 3321 and 3325 (Trademarks), made by Chisso Corporation] (5)

[FM4411, 4421 and 4425 (Trademarks), made by Chisso Corporation] (6)

[FM5511, 5521 and 5525 (Trademarks), made by Chisso Corporation] (7)

[FM0411, 0421 and 0425 (Trademarks), made by Chisso Corporation] (8)

[FM0511, 0521 and 0525 (Trademarks), made by Chisso Corporation] (9)

[FM0711, 0721 and 0725 (Trademarks), made by Chisso Corporation]

[0074] In addition, the following reactive silicone materials which arecommercially available from Shin-Etsu Chemical Co., Ltd., can beemployed in the present invention:

[0075] amino-modified silicone compounds such as “X-22-161A”, “KF867”and “KF865” (Trademarks),

[0076] epoxy-modified silicone compounds such as “X-22-163B” and“X-22-169AS” (Trademarks),

[0077] carboxy-modified silicone compound such as “X-22-162C”(Trademark),

[0078] Carbitol-modified silicone compound such as “KF-6002”(Trademark),

[0079] methacryl-modified silicone compounds such as “X-22-164C” and“X-22-5002” (Trademarks),

[0080] mercapto-modified silicone compound such as “X-22-980”(Trademark),

[0081] phenol-modified silicone compound such as “X-22-165B”(Trademark),

[0082] one-side terminal reactive silicone materials such as“X-22-174DX” and “X-22-174D” (Trademarks), andhetero-functional-group-modified silicone compounds such as “KF862”,“X-22-3667”, “X-22-3959A”, “KF99” and “FM-1125” (Trademarks).

[0083] Examples of silicone RTV (Room Temperature Vulcanizing) siliconerubbers are one-pack type RTV rubbers such as “KE41”, “KE42”, “KE40RTV”,“KE3491” and “KE3492” (Trademarks) made by Shin-Etsu Chemical Co., Ltd.,and two-pack type RTV silicone rubbers such as “KE119”, “KE108” and“KE110 Gel” (Trademarks) made by Shin-Etsu Chemical Co., Ltd.

[0084] These silicone rubbers are used with the viscosity and physicalproperties thereof being adjusted so as to make them suitable for use intoner or ink or the like by changing the amount of a curing agent or asilicone oil for dilution to be added thereto.

[0085] In the present invention, the reactive silicone material can beemployed in the carrier liquid. The recording performance of the liquidrecording material of the present invention can be further improved byuse of a polymerizable vinyl monomer in the combination with thereactive silicone material in the carrier liquid.

[0086] More specifically, it is preferable that the weight ratio of thepolymerizable vinyl monomer/the reactive silicone material be in therange of 1/0.01 to 1/9, more preferably, in the range of 1/0.1 to 1/7.When the amount of the reactive silicone material is less than 0.01 interms of the above-mentioned weight ratio, the dispersibility orsolubility of the polymerized resin in the silicone solvent is reduced,while when the amount of the reactive silicone material is more than 9in terms of the above-mentioned weight ratio, the adhesive force of thepolymerized resin is reduced. In accordance with the characteristicsrequired, the combination of the polymerizable vinyl monomer and thereactive silicone material in terms of their kinds can be changed.

[0087] In the present invention, a carrier liquid comprising thereactive silicone material and a silicone oil which is mixed with thereactive silicone material can also be employed. More specifically, apoly-dialkylsiloxane and a cyclic polydialkylsiloxane with a kinematicviscosity of 0.01 to 1,000,000 centistokes, preferably, with a kinematicviscosity of 1 to 10,000 centistokes at 25° C., are preferable.

[0088] Examples of the above-mentioned polymerizable vinyl monomer arevinyl monomers for homopolymerization, and monomers for copolymerizationin the presence of a cross-linking agent and other monomers.

[0089] Specific examples of the vinyl monomers are (meth)acrylic acid,maleic acid, maleic anhydride, itaconic acid, itaconic anhydride,fumaric acid, cinnamic acid, crotonic acid, vinylbenzoic acid,2-methacryloxyethyl succinic acid, 2-methacryloxyethyl maleic acid,2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyltrimellitic acid, vinylsulfonic acid, allyl sulfonic acid, styrenesulfonic acid, 2-sulfoethyl methacrylate,2-acrylamide-2-methylpropanesulfonic acid, 3-chloroamidephosxipropylmethacrylate, 2-methacryloxyethyl acid phosphate, hydroxystyrene,glycidyl methacrylate, 2-hydroxyethyl (meth)acrylate,2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,2-hydroxy-3-propylmethacrylate, 2-chloroethyl (meth)acrylate,2,3-dibromopropyl (meth)acrylate, (meth)acrylonitrile, vinyl chloride,isobutyl-2-cyanoacrylate, 2-cyanoethylacrylate, ethyl-2-cyanoacrylate,methacrylacetone, tetrahydrofurfuryl methacrylate,trifluoroethylmethacrylate, p-nitrostyrene, vinylbenzene, ethyleneglycoldi(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycoltri(meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate,tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipropylene-glycol di(meth)acrylate,trimethylolhexane tri-(meth)acrylate, pentaerythritoltetra(meth)acrylate, 1,3-dibutylene glycol di(meth)acrylate,trimethylolethane tri(meth)acrylate, N-methylaminoethyl (meth)acrylate,N-ethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylateN,N-diethylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl acrylate,N-phenylaminoethyl methacrylate, N,N-diphenylaminoethyl methacrylate,aminostyrene, dimethylaminostyrene, N-methylaminoethyl-styrene,dimethylaminoethoxystyrene, diphenylaminoethyl-styrene,N-phenylaminoethylstyrene, vinylpyrrolidone, 2-N-piperidylethyl(meth)acrylate, 2-vinylpyridine, 4-vinylpyridine,2-vinyl-6-methylpyridine, acrylamide, methacrylamide, N,N-dimethylmethacrylamide, N,N-dibutyl methacrylamide, 2-ethylhexyl (meth)acrylate,octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl(meth)acrylate, stearyl (meth)acrylate, vinyl laurate, laurylmethacrylamide, stearyl methacrylamide, methoxyethyl (meth)acrylate,ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methyl(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl(meth)acrylate, styrene, vinyltoluene, and vinyl acetate.

[0090] It is preferable that the amount of these polymerizable monomersbe employed in an amount of 0.1 to 50 parts by weight to 100 parts byweight of the reactive silicone material.

[0091] In the present invention, the following compounds can be employedas a dispersing agent or a charge control agent: metal titanate couplingagents such as tetra-n-butoxy titanium, tetraisopropoxy titanium,isopropyl-triisostearoyl titanate, bis(dioctylpyrophosphate)-ethylenetitanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyltri(dioctylphosphate) titanate, isopropyl tridodecylbenzene sulfonyltitanate, diisostearoylethylene titanate, isopropyltrioctyl titanate,bis(dioctylpyrophosphate)oxyacetate titanate, isopropyl tricumylphenyltitanate, and dicumylphenyloxyacetate titanate. Those metal couplingagents may be used alone or in combination.

[0092] In addition, manganese octylate, cobalt, nickel, calcium,manganese naphthenate can be employed.

[0093] Furthermore, when necessary, for example, the following chargecontrol agents can also be added to the liquid recording material of thepresent invention: lecithin, petroleum calcium sulfonate, sodium dioctylsulfonate, alkylalanine, calcium alkylnaphthalene-sulfonate, anddi-2-ethylhexyl sodium sulfosuccinate.

[0094] Particularly good and suitable coloring agents for use in thepresent invention are a disazo yellow pigment, a carmine pigment, aquinacridone pigment and a phthalocyanine pigment. These pigments alsohave good stability. However, the reason why these pigments have such agood stability has not yet been thoroughly analyzed, but it isconsidered that these pigments contain appropriate polar groups in themolecules thereof, so that the charge control agents and resins can beproperly adsorbed by the pigments and therefore no polarity biasing iscaused in the toner particles contained in the liquid recording materialof the present invention by discharge current applied thereto.

[0095] Specific examples of each of the above-mentioned pigments are asfollows:

[0096] Examples of the disazo yellow pigment include Pigment Yellow 12,Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow55, Pigment Yellow 81, and Pigment Yellow 83.

[0097] Examples of the carmine pigment of magenta include Pigment Red 5,Pigment Red 57, Pigment Red 60, Pigment Red 114, Pigment Red 146, andPigment Red 185.

[0098] Examples of the quinacridone pigment include Pigment Red 112 andPigment Red 209.

[0099] Examples of the phthalocyanine pigment include Pigment Blue 15:1(α-phthalocyanine), Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue15:6, and Pigment Blue 16.

[0100] Furthermore, the following pigments represented by formulae (1)to (3) are particularly preferable for use in the present invention:

[0101] Compound No. 1-1:

[0102] —OCH₃ at position 1 in formula (1)

[0103] Compound No. 1-2:

[0104] —OCH₃ at positions 1 and 7 in formula (1)

[0105] Compound No. 1-3:

[0106] —Cl at position 10 in formula (1)

[0107] Compound No. 1-4:

[0108] —C₂H₅ at position 3 in formula (1)

[0109] Compound No. 1-5:

[0110] —C₄H₉ at position 3 in formula (1)

[0111] Compound No. 1-6:

[0112] —COC₂H₅ at position 6 in formula (1)

[0113] Compound No. 1-7:

[0114] —COC₄H₉ at position 6 in formula (1), and

[0115] Compound No. 1-8:

[0116] —COOH at position 5 in formula (1)

[0117] Compound No. 2-1:

[0118] —OH at position 2 and position 11 in formula (2)

[0119] Compound No. 2-2:

[0120] —COOH at position 2 in formula (2)

[0121] Compound No. 2-3:

[0122] —CH₃ at position 1 in formula (2)

[0123] Compound No. 2-4:

[0124] —OCH₃ at position 10, and

[0125] —OH at position 2 in formula (2)

[0126] Compound No. 2-5:

[0127] —OH at position 12, and —CH₃ at position 4 in formula (2)

[0128] Compound No. 2-6:

[0129] the same as Compound No. 2-1, provided that Ba^(2⊕) is atposition 13 in formula (2)

[0130] Compound No. 2-7:

[0131] the same as Compound No. 2-2, provided that Zn^(2⊕) is atposition 13 in formula (2)

[0132] Compound No. 2-8:

[0133] the same as Compound No. 2-4, provided that Ba^(2⊕) is atposition 13 in formula (2)

[0134] Compound No. 3-1:

[0135] R¹ and R¹⁴: —Cl

[0136] R² to R¹³, R¹⁵, and R¹⁶: —H in formula (3)

[0137] Compound No. 3-2:

[0138] R¹ and R¹⁴: —Br

[0139] R² to R¹³ R¹⁵, and R¹⁶: —H in formula (3)

[0140] Compound No. 3-3:

[0141] R¹, R⁶, R¹², and R¹⁴:—Cl

[0142] R² to R⁵, R⁷ to R¹¹, R¹³, R¹⁵, and R¹⁶: —H in formula (3)

[0143] Compound No. 3-4:

[0144] the same as Compound No. 3-1, provided that the metal Cu isreplaced by Zn in formula (3)

[0145] Compound No. 3-5:

[0146] the same as Compound No. 3-2, provided that the metal Cu isreplaced by Ca in formula (3)

[0147] Compound No. 3-6:

[0148] the same as Compound No. 3-3, provided that the metal Cu isreplaced by Ba in formula (3)

[0149] Compound No. 3-7:

[0150] R¹, R⁶, R¹⁰, and R¹⁴: —OCH₃

[0151] R² to R⁶, R⁷ to R⁹, R¹¹ to R¹³, R¹⁵ and R¹⁶: —H in formula (3)

[0152] Compound No. 3-8:

[0153] R¹, R⁶, R¹⁰, and R¹⁴: —OC₂H₅

[0154] R to R¹, R¹ to R⁹, R¹¹ to R¹³, R¹⁵ and R¹⁶: —H in formula (3)

[0155] The liquid recording material of the present invention, whichalso may be referred to as a liquid developer, comprises the carrierliquid, the coloring agent, the resin, and the reactive siliconematerial, and is prepared, with the addition of a charge control agentthereto when necessary, in such a manner that toner particles with anaverage particle size of 20 um or less, preferably in the range of 0.2to 10 μm, are dispersed therein in a dispersion mixer such as a keddymill, a bead mill, an attritor, a ball mill, a roll mill or a three-rollmill.

[0156] The reactive silicone material for use in the present inventionis capable of highly dispersing pigments therein, so that even when theliquid recording material with toner particles having a reduced particlesize is allowed to stand for an extended period of time, the tonerparticles are difficult to sediment. Furthermore, by use of the reactivesilicone material, it is possible to provide recording materials such asan electrophotographic developer capable of producing excellent imagedensity and color characteristics, in particular, high glossiness, inkjet printing inks, and printing inks. Furthermore, by use of thereactive silicone material in dyes, dyes with high glossiness, waterresistance and solvent resistance, can be obtained.

[0157] In the present invention, the recording material comprising thereactive silicone material can be subjected to an external stimulus suchas light stimulus, heat stimulus or electric stimulus (which is referredto as a method A), or can be allowed to react with a functional materialsuch as an oxidizing agent, a reducing agent, an estrification agent, acoupling agent, a polymerization initiator, crosslinking agent, or agelling agent (which is referred to as a method B), or can be subjectedto the treatment in which the method A and the method B are combined,whereby the reactive silicone material can be polymerized.

[0158] Alternatively, a sheet of paper or the cellulose of the paper iscoated with the above-mentioned functional material employed in themethod B, and images are printed on the paper, using the recordingmaterial comprising the reactive silicone material of the presentinvention, which may be in the form of an electrophotographic developer,or in the form of an ink jet printing ink or a printing ink, and theprinted images are fixed to the paper, using the chemical reaction orphysical adsorption of the reactive silicone material with the paper.

[0159] The liquid recording material of the present invention, which maybe in the form of a liquid electrophotographic developer, can beproduced by kneading and dispersing the carrier liquid, the coloringagent, the resin, when necessary, with the addition of conventionaladditives, in the presence of the reactive silicone material, which mayserve as the carrier liquid as well, in a mixer such as a ball mill oran attritor.

[0160] It is preferable that the amount of the resin be in the range of0.01 to 10 parts by weight to 1 part by weight of the coloring agent.

[0161] Specific examples of the coloring agent for use in the presentinvention are:

[0162] carbon black such as “MA-100”, “#44” and “#33” (Trademarks) madeby Mitsubishi Chemical Corporation, “Raben 1250” and “Raben 1020”(Trademarks) made by Columbian Carbon Ltd., and “Black Pearl L” and“Black Pearl 1100” (Trademarks) made by Cabot Corporation, “Printex 55”and “Special Black 4” (Trademarks) made by Degussa Japan Co., Ltd.; andorganic pigments such as insoluble azo pigments, soluble azo pigments,phthalo-cyanine pigments, isoindolinone higher pigments, quinacridonehigher pigments, and perinone•perylene higher pigments.

[0163] Specific examples of the resin for use in the present inventionare ethyl cellulose, linseed-oil-modified alkyd resin, acrylic ormethacrylic ester resin, polystyrene, silcone-acryl copolymer, siliconeresin, silicone-(meth)acryl copolymer, block polymer or graft polymer,polyolefin copolymer, poly(vinyl chloride) resin, chlorinatedpolypropylene, polyamide resin, coumarone-indene resin, rosin-modifiedresin, and alkylphenol-modified xylene resin.

[0164] It is preferable that the reactive silicone material used as thecarrier liquid have a viscosity of 0.5 to 10,000 CS, more preferably aviscosity of 5 to 5000 CS, in terms of the physical properties thereof.

EXAMPLE 1

[0165] A mixture of the following components was dispersed in anattritor for 2 hours: Parts by Weight Carbon black (Trademark “#44”, 100made by Mitsubishi Chemical Corporation) Lauryl methacrylate/methyl  50methacrylate (60/40) copolymer Reactive silicone material 500 (Trademark“X22-5002”, made by Shin-Etsu Chemical Co., Ltd.)

[0166] Thus, a liquid recording material No. 1 of the present invention,which can be used as an electrophotographic liquid developer, with atoner particle size of 1.26 μm, was obtained.

[0167] By use of the liquid recording material No. 1, images wereformed, using a commercially available electrophotographic copyingmachine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.). As aresult, excellent copy images with an image density of 1.24, abackground density of 0.01, and a resolution of 6.3 lines/mm, wereobtained. The image fixing ratio of the images measured by the clockmeter method was 71%.

EXAMPLE 2

[0168] 100 parts by weight of carbon black (Trademark “Mitsubishi#MA-11”, made by Mitsubishi Chemical Corporation) and 500 parts byweight of rosin-modified maleic acid resin were kneaded at 150° C. in akneader, whereby a coloring agent A was obtained.

[0169] To 100 parts by weight of the thus obtained coloring agent A, 0.5parts by weight of cobalt naphthenate and 500 parts by weight of areactive silicone “FM-1111” (Trademark) made by Chisso Corporation wereadded. The mixture was dispersed in an attritor for 3 hours, whereby aliquid recording material No. 2 of the present invention, in the form ofa liquid toner with an average toner particle size of 1.52 μm, wasobtained.

[0170] By use of the liquid recording material No. 2, images wereformed, using a commercially available electrophotographic copyingmachine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.). As aresult, excellent copy images with an image density of 1.26, abackground density of 0.01, a resolution of 6.3 lines/mm, and aglossiness of 26% were obtained. The image fixing ratio of the imageswas 80%.

[0171] For comparison, the same procedure of producing the liquidrecording material No. 2 as mentioned above was repeated except that thereactive silicone “FM-1111” (Trademark) employed in the above wasreplaced by a non-reactive silicone “KF96-50CS” (Trademark), made byShin-Etsu Chemical Co., Ltd., whereby a comparative liquid recordingmaterial was prepared. The average toner particle size of thecomparative liquid recording material was 13.50 μm.

[0172] By use of the comparative liquid recording material, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 0.66,a resolution of 4.3 lines/mm, and a glossiness of 4.1%, which wereconspicuously inferior to the images obtained by the liquid recordingmaterial No. 2 of the present invention, were obtained. It is consideredthat this was because the average toner particle size of the comparativeliquid recording material which was produced, using the non-reactivesilicone “KF96-50CS” (Trademark), was as large as 13.50 μm and thereforethe charging of the toner particles was not uniform.

EXAMPLE 3

[0173] The same procedure of producing the liquid recording material No.1 as in Example 1 was repeated except that the reactive siliconematerial (Trademark “X22-5002”, made by Shin-Etsu Chemical Co., Ltd.)employed in Example 1 was replaced by a reactive silicone “KF99”(Trademark), made by Shin-Etsu Chemical Co., Ltd. and that 5.0 parts byweight of a silane coupling agent were added thereto, whereby a liquidrecording material No. 3 of the present invention was produced. Theaverage toner particle size of the liquid recording material No. 3 was0.29 μm.

[0174] By use of the liquid recording material No. 3, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.23,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 86%.

EXAMPLE 4

[0175] The same procedure of producing the liquid recording material No.1 as in Example 1 was repeated except that the reactive siliconematerial (Trademark “X22-5002”, made by Shin-Etsu Chemical Co., Ltd.)employed in Example 1 was replaced by a reactive silicone “FP2231”(Trademark), made by Chisso Corporation, whereby a liquid recordingmaterial No. 4 of the present invention was produced. The average tonerparticle size of the liquid recording material No. 4 was 0.32 μm.

[0176] By use of the liquid recording material No. 4, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.26,a background density of 0.01, and a resolution of 7.2 lines/mm wereobtained. The image fixing ratio of the images was 76%.

EXAMPLE 5

[0177] The same procedure of producing the liquid recording material No.2 as in Example 2 was repeated except that the reactive silicone“FM-1111” (Trademark) made by Chisso Corporation employed in Example 2was replaced by a reactive silicone “FP2231” (Trademark), made by ChissoCorporation, whereby a liquid recording material No. 5 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 5 was 0.43 μm.

[0178] By use of the liquid recording material No. 5, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.31,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 74%.

EXAMPLE 6

[0179] The same procedure of producing the liquid recording material No.2 as in Example 2 was repeated except that the reactive silicone“FM-1111” (Trademark) made by Chisso Corporation employed in Example 2was replaced by a reactive silicone “FM3311” (Trademark), made by ChissoCorporation, whereby a liquid recording material No. 6 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 6 was 0.21 μm.

[0180] By use of the liquid recording material No. 6, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.33,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 77%.

EXAMPLE 7

[0181] The same procedure of producing the liquid recording material No.2 as in Example 2 was repeated except that the reactive silicone“FM-1111” (Trademark) made by Chisso Corporation employed in Example 2was replaced by a reactive silicone “FM4421” (Trademark), made by ChissoCorporation, whereby a liquid recording material No. 7 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 7 was 0.26 μm.

[0182] By use of-the liquid recording material No. 7, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of-1.30,a background density of 0.01, and a resolution of 7.2 lines/mm wereobtained. The image fixing ratio of the images was 76%.

EXAMPLE 8

[0183] The same procedure of producing the liquid recording material No.1 as in Example 1 was repeated except that the reactive siliconematerial (Trademark “X22-5002”, made by Shin-Etsu Chemical Co., Ltd.)employed in Example 1 was replaced by a reactive silicone “FM0511”(Trademark), made by Chisso Corporation, whereby a liquid recordingmaterial No. 8 of the present invention was produced. The average tonerparticle size of the liquid recording material No. 8 was 0.38 μm.

[0184] By use of the liquid recording material No. 8, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.36,a background density of. 0.01, and a resolution of 7.2 lines/mm wereobtained. The image fixing ratio of the images was 76%.

EXAMPLE 9

[0185] The same procedure of producing the liquid recording material No.3 as in Example 3 was repeated except 100 parts by weight of laurylmethacrylate were added to the formulation for the liquid recordingmaterial No. 3, whereby a liquid recording material No. 9 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 9 was 0.58 μm.

[0186] By use of the liquid recording material No. 9, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.25,a background density of 0.02, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 82%.

EXAMPLE 10

[0187] The same procedure of producing the liquid recording material No.4 as in Example 4 was repeated except that the coloring agent, namely,carbon black (Trademark “#44” made by Mitsubishi Chemical Corporation),employed in Example 4 was replaced by Carmine 6B, whereby a liquidrecording material No. 10 of the present invention was produced. Theaverage toner particle size of the liquid recording material No. 10 was0.19 μm.

[0188] By use of the liquid recording material No. 10, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.30,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 78%.

EXAMPLE 11

[0189] The same procedure of producing the liquid recording material No.5 as in Example 5 was repeated except that 30 wt. % of the reactivesilicone “FP2231” (Trademark), made by Chisso Corporation employed inExample 5 was replaced by “Isopar H” (Trademark), made by Exxon ChemicalJapan Ltd., whereby a liquid recording material No. 11 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 11 was 0.63 μm.

[0190] By use of the liquid recording material No. 11, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.18,a background density of 0.03, and a resolution of 5.6 lines/mm wereobtained. The image fixing ratio of the images was 75%.

EXAMPLE 12

[0191] The same procedure of producing the liquid recording material No.5 as in Example 5 was repeated except that 30 wt. % of the reactivesilicone “FP2231” (Trademark), made by Chisso Corporation employed inExample 5 was replaced by soybean oil, whereby a liquid recordingmaterial No. 12 of the present invention was produced. The average tonerparticle size of the liquid recording material No. 12 was 0.88 μm.

[0192] By use of the liquid recording material No. 12, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.24,a background density of 0.02, and a resolution of 5.6 lines/mm wereobtained. The image fixing ratio of the images was 71%.

EXAMPLE 13

[0193] The same procedure of producing the liquid recording material No.5 as in Example 5 was repeated except that 30 wt. % of the reactivesilicone “FP2231” (Trademark), made by Chisso Corporation employed inExample 5 was replaced by isopropyl myristate, whereby a liquidrecording material No. 13 of the present invention was produced. Theaverage toner particle size of the liquid recording material No. 13 was0.69 μm.

[0194] By use of the liquid recording material No. 13, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.26,a background density of 0.02, and a resolution of 5.6 lines/mm wereobtained. The image fixing ratio of the images was 70%.

EXAMPLE 14

[0195] The same procedure of producing the liquid recording material No.2 as in Example 2 was repeated except that 20 wt. % of the reactivesilicone “FM-1111” (Trademark) made by Chisso Corporation employed inExample 2 was replaced by a non-reactive silicone oil “KF96-100CS”(Trademark), made by Shin-Etsu Chemical Co., Ltd., whereby a liquidrecording material No. 14 of the present invention was produced. Theaverage toner particle size of the liquid recording material No. 14 was2.43 μm.

[0196] By use of the liquid recording material No. 14, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.26,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 62%.

EXAMPLE 15

[0197] The same procedure of producing the liquid recording material No.2 as in Example 2 was repeated except 13 parts by weight of apolymerization initiator (Trademark “KAYA ESTER-O”) were added to theformulation for the liquid recording material No. 2, whereby a liquidrecording material No. 15 of the present invention was produced. Theaverage toner particle size of the liquid recording material No. 15 was0.38 μm.

[0198] By use of the liquid recording material No. 15, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.28,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 88%.

EXAMPLE 16

[0199] The same procedure of producing the liquid recording material No.13 as in Example 13 was repeated except 3 parts by weight of calciumoleate were added to the formulation of the liquid recording materialNo. 13, whereby a liquid recording material No. 16 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 16 was 0.82 μm.

[0200] By use of the liquid recording material No. 16, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400I”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.30,a background density of 0.01, and a resolution of 5.3 lines/mm wereobtained. The image fixing ratio of the images was 76%.

EXAMPLE 17

[0201] The same procedure of producing the liquid recording material No.12 as in Example 12 was repeated except 5 parts by weight of cobaltnaphthenate were added to the formulation for the liquid recordingmaterial No. 12, whereby a liquid recording material No. 17 of thepresent invention was produced. The average toner particle size of theliquid recording material No. 17 was 0.64 μm.

[0202] By use of the liquid recording material No. 17, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.38,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 81%.

EXAMPLE 18

[0203] The same procedure of producing the liquid recording material No.5 as in Example 5 was repeated except that 30 wt. % of the reactivesilicone “FP2231” (Trademark), made by Chisso Corporation employed inExample 5 was replaced by tung oil and that 5 parts by weight of cobaltnaphthenate were added to this formulation, whereby a liquid recordingmaterial No. 18 of the present invention was produced. The average tonerparticle size of the liquid recording material No. 18 was 0.58 μm.

[0204] By use of the liquid recording material No. 18, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.29,a background density of 0.02, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 85%.

EXAMPLE 19

[0205] The same procedure of producing the liquid recording material No.18 as in Example 18 was repeated except that the tung oil employed inExample 18 was replaced by a silicone RTV rubber “KE110 Gel” (Trademark)containing 0.5 wt. % of a curing agent made by Shin-Etsu Chemical Co.,Ltd., whereby a liquid recording material No. 19 of the presentinvention was produced. The average toner particle size of the liquidrecording material No. 19 was 0.53 μm.

[0206] By use of the liquid recording material No. 19, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.32,a background density of 0.01, and a resolution of 7.2 lines/mm wereobtained. The image fixing ratio of the images was 88%.

EXAMPLE 20

[0207] The same procedure of producing the liquid recording material No.1 as in Example 1 was repeated except that the laurylmethacrylate/methyl methacrylate (60/40) copolymer employed in Example 1was replaced by a silicone rubber “KE108” (Trademark) made by Shin-EtsuChemical Co., Ltd., whereby a liquid recording material No. 20 of thepresent invention was produced. The average toner particle size of theliquid recording material No. 20 was 0.38 μm.

[0208] By use of the liquid recording material No. 20, images wereformed, using the same commercially available electrophotographiccopying machine (Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) asmentioned above. As a result, copy images with an image density of 1.33,a background density of 0.01, and a resolution of 6.3 lines/mm wereobtained. The image fixing ratio of the images was 90%. TABLE 2 (1)Coloring Agent (2) Resin Toner Resolu- Image (3) Reactive SiliconeParticle Back- tion Fixing Ex. Material Size ground Image (lines/ RatioNo. (4) Additional Component (μm) Density Density mm) (%) 1 (1) CarbonBlack 1.26 0.01 1.24 6.3 71 (2) Lauryl methacrylate/ Methyl methacrylate(60/40) copolymer (3) “X22-5002” 2 (1) Carbon Black 1.52 0.01 1.26 6.380 (2) Rosin-modified maleic acid resin (3) “FM 1111“ 3 (1) Carbon Black0.29 0.01 1.23 6.3 86 (2) Lauryl methacrylate/ Methyl methacrylate(60/40) copolymer (3) “KF99” + Silane coupling agent 4 (1) Carbon Black0.32 0.01 1.26 7.2 76 (2) Lauryl methacrylate/ Methyl methacrylate(60/40) copolymer (3) “FP2231” 5 (1) Carbon Black 0.43 0.01 1.31 6.3 74(2) Rosin-modified maleic acid resin (3) “FP2231” 6 (1) Carbon Black0.21 0.01 1.33 6.3 77 (2) Rosin-modified maleic acid resin (3) “FM3311”7 (1) Carbon Black 0.26 0.01 1.30 7.2 76 (2) Rosin-modified maleic acidresin (3) “FM4421” 8 (1) Carbon Black 0.38 0.01 1.36 7.2 76 (2) Laurylmethacrylate/ Methyl methacrylate (60/40) copolymer (3) “FM0511” 9 (1)Carbon Black 0.58 0.02 1.25 6.3 82 (2) Lauryl methacrylate/ Methylmethacrylate (60/40) copolymer + Lauryl methacrylate (3) “KF99” + Silanecoupling agent 10 (1) Carmine 6B 0.19 0.01 1.30 6.3 78 (2) Laurylmethacrylate/ Methyl methacrylate (60/40) copolymer (3) “FP2231” 11 (1)Carbon Black 0.63 0.03 1.18 5.6 75 (2) Rosin-modified maleic acid resin(3) “FP2231” (70%) + “Isopar H” (30%) 12 (1) Carbon Black 0.88 0.02 1.245.6 71 (2) Rosin-modified maleic acid resin (3) “FP2231” (70%) + SoybeanOil (30%) 13 (1) Carbon Black 0.69 0.02 1.26 5.6 70 (2) Rosin-modifiedmaleic acid resin (3) “FP2231” (70%) + Isopropyl myristate (30%) 14 (1)Carbon Black 2.43 0.01 1.26 6.3 62 (2) Rosin-modified maleic acid resin(3) “FM-1111” (80%) + “KF96-100CS” (20%) 15 (1) Carbon Black 0.38 0.011.28 6.3 88 (2) Rosin-modified maleic acid resin (3) “FM-1111” + “KAYAESTER-O” 16 (1) Carbon Black 0.82 0.01 1.30 5.3 76 (2) Rosin-modifiedmaleic acid resin (3) “FP2231” (70%) + Isopropyl myristate (30%) (4)Calcium oleate 17 (1) Carbon Black 0.64 0.01 1.38 6.3 81 (2)Rosin-modified maleic acid resin (3) “FP2231” (70%) + Soybean Oil (30%)(4) Cobalt naphthenate 18 (1) Carbon Black 0.58 0.02 1.29 6.3 85 (2)Rosin-modified maleic acid resin (3) “FP2231” (70%) + Tung Oil (30%) (4)Cobalt naphthenate 19 (1) Carbon Black 0.53 0.01 1.32 7.2 88 (2)Rosin-modified maleic acid resin (3) “FP2231” (70%) + “KE110 Gel” (30%)(4) Cobalt naphthenate 20 (1) Carbon Black 0.38 0.01 1.33 6.3 90 (2)“KE108” (3) “X22-5002”

EXAMPLE 21

[0209] The following components were dispersed in a ball mill for 48hours, whereby an image fixing and oil absorption layer formation liquidwas prepared: Parts by Weight Titanium oxide 100 Isopropyl alcohol 500Calcium oleate  30 Silane coupling agent  50

[0210] The thus prepared image fixing and oil absorption layer formationliquid was coated with a thickness of 3 μm on a sheet of high qualitypaper, whereby an image transfer sheet was prepared.

[0211] A liquid recording material was prepared by the same procedure ofproducing the liquid recording material No. 1 as in Example 1 exceptthat the reactive silicone material (Trademark “X22-5002”, made byShin-Etsu Chemical Co., Ltd.) employed in Example 1 was replaced by areactive silicone “KF99” (Trademark), made by Shin-Etsu Chemical Co.,Ltd.

[0212] By use of this liquid recording material, images were formed, onthe above prepared image transfer sheet, using the same commerciallyavailable electrophotographic copying machine (Trademark “RICOPYFT-400i”, made by Ricoh Co., Ltd.) as mentioned above. As a result, copyimages with an image density of 1.28, a background density of 0.01, anda resolution of 7.2 lines/mm were obtained. The image fixing ratio ofthe images was 87%.

[0213] Even immediately after making copies, no smearing was caused inthe copies made.

EXAMPLE 22

[0214] By use of the liquid recording material No. 3 prepared in Example3, an image was formed and was then subjected to flash image fixing,using a commercially available electrophotographic copying machine(Trademark “RICOPY FT-400i”, made by Ricoh Co., Ltd.) which was modifiedto be capable of performing the flash image fixing. As a result, imageswere formed with a background density of 0.01, an image density of 1.36,a resolution of 9.2 lines/mm, and an image fixing ratio of 92%.

EXAMPLE 23

[0215] The liquid recording material No. 17 prepared in Example 17 andthe liquid recording material No. 18 prepared in Example 18 were eachused as a printing ink for a commercially available simplified printer“PRIPORT” (Trademark), made by Ricoh Co., Ltd. The result was that boththe liquid recording materials No. 17 and No. 18 exhibited excellentimage fixing performance and image quality.

EXAMPLE 24

[0216] The liquid recording material No. 2 prepared in Example 2 wasevaluated, using a voltage application type ink jet system. The resultwas that images with an image density of 1.26, and an image fixing ratioof 70% were obtained.

[0217] Japanese Patent Application No. 11-003488 filed Jan. 8, 1999, ishereby incorporated by reference.

What is claimed is:
 1. A liquid recording material comprising a carrierliquid, a resin, a coloring agent, and a reactive silicone material. 2.The liquid recording material as claimed in claim 1, wherein saidreactive silicone material comprises a reactive silicone compound thatcontains in the molecule thereof at least one group selected from thegroup consisting of vinyl group, amino group, hydroxyl group, epoxygroup, isocyanate group, and an active hydrogen.
 3. The liquid recordingmaterial as claimed in claim 1, wherein said carrier liquid comprisessaid reactive silicone material.
 4. The liquid recording material asclaimed in claim 1, wherein said resin comprises said reactive siliconematerial.
 5. The liquid recording material as claimed in claim 1,wherein said coloring agent comprises said reactive silicone material.6. The liquid recording material as claimed in claim 3, wherein saidreactive silicone material comprises a silicone RTV rubber.
 7. Theliquid recording material as claimed in claim 4, wherein said reactivesilicone material comprises a silicone RTV rubber.
 8. The liquidrecording material as claimed in claim 5, wherein said reactive siliconematerial comprises a silicone RTV rubber.
 9. The liquid recordingmaterial as claimed in claim 1, wherein said carrier liquid comprisessaid reactive silicone material and a polymerizable vinyl monomer, withthe weight ratio of said reactive silicone material: said polymerizablevinyl monomer being in a range of (0.01 to 9):
 1. 10. The liquidrecording material as claimed in claim 1, wherein said carrier liquidcomprises said reactive silicone material and an aliphatic hydrocarbon.11. The liquid recording material as claimed in claim 1, wherein saidcarrier liquid comprises said reactive silicone material and a vegetableoil.
 12. The liquid recording material as claimed in claim 1, whereinsaid carrier liquid comprises said reactive silicone material and asynthetic oil.
 13. The liquid recording material as claimed in claim 1,wherein said carrier liquid comprises said reactive silicone materialand a silicone oil.
 14. The liquid recording material as claimed inclaim 1, wherein said carrier liquid further comprises a polymerizationinitiator.
 15. The liquid recording material as claimed in claim 1,wherein said carrier liquid further comprises at least one componentselected from the group consisting of a gelling agent and across-linking agent.
 16. The liquid recording material as claimed inclaim 1, wherein said coloring agent is one coloring agent selected fromthe group consisting of a yellow coloring agent, a magenta coloringagent, a cyan coloring agent, and a black coloring agent.
 17. The liquidrecording as claimed in claim 16, wherein said yellow coloring agentcomprises a disazo pigment, said magenta coloring agent comprises aquinacridone pigment or a carmine pigment, said cyan coloring agentcomprises copper phthalocyanine, and said black coloring agent comprisescarbon black.
 18. The liquid recording material as claimed in claim 1,further comprising at least one component selected from the groupconsisting of an oxidizing agent, a reducing agent, an esterificationagent, a coupling agent, a gelling agent, and a polymerizationinitiator.
 19. An image transfer material comprising at least on thesurface thereof at least one component selected from the groupconsisting of an oxidizing agent, a reducing agent, an esterificationagent, a coupling agent, a gelling agent, and a polymerizationinitiator.
 20. A method of fixing an image developed by using a liquidrecording material comprising a carrier liquid, a resin, a coloringagent, and a reactive silicone material, on an image transfer materialcomprising at least on the surface thereof at least one componentselected from the group consisting of an oxidizing agent, a reducingagent, an esterification agent, a coupling agent, a gelling agent, and apolymerization initiator, with the application of corona charge theretoas an external stimulus.